CN1956988A - Mono-, oligo- and polythieno[3,2-b]thiophenes - Google Patents
Mono-, oligo- and polythieno[3,2-b]thiophenes Download PDFInfo
- Publication number
- CN1956988A CN1956988A CNA2005800159680A CN200580015968A CN1956988A CN 1956988 A CN1956988 A CN 1956988A CN A2005800159680 A CNA2005800159680 A CN A2005800159680A CN 200580015968 A CN200580015968 A CN 200580015968A CN 1956988 A CN1956988 A CN 1956988A
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- CN
- China
- Prior art keywords
- polymkeric substance
- thiophene
- oligopolymer
- monomer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930192474 thiophene Natural products 0.000 title claims abstract description 32
- 150000003577 thiophenes Chemical class 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 69
- 239000004065 semiconductor Substances 0.000 claims abstract description 23
- 230000005669 field effect Effects 0.000 claims abstract description 12
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 230000003287 optical effect Effects 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 101
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000010408 film Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- -1 Amino Chemical group 0.000 claims description 7
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000002152 alkylating effect Effects 0.000 claims description 4
- 150000003851 azoles Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 108091028043 Nucleic acid sequence Proteins 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005605 benzo group Chemical group 0.000 claims description 3
- 239000008194 pharmaceutical composition Substances 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000012788 optical film Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- 239000010410 layer Substances 0.000 description 26
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 23
- 238000003756 stirring Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 238000010926 purge Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000000944 Soxhlet extraction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000002019 doping agent Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- UAKVLZIHQBWZFN-UHFFFAOYSA-N 5-dodecylthieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=C(CCCCCCCCCCCC)S2 UAKVLZIHQBWZFN-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- 239000004990 Smectic liquid crystal Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 125000001246 bromo group Chemical group Br* 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 description 5
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 125000003638 stannyl group Chemical group [H][Sn]([H])([H])* 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- VAAGULPSFSBRJU-UHFFFAOYSA-N 3,4-didecylthiophene Chemical compound CCCCCCCCCCC1=CSC=C1CCCCCCCCCC VAAGULPSFSBRJU-UHFFFAOYSA-N 0.000 description 2
- QFZLOYZIBDWMLB-UHFFFAOYSA-N 3,6-dioctylthieno[3,2-b]thiophene Chemical compound CCCCCCCCC1=CSC2=C1SC=C2CCCCCCCC QFZLOYZIBDWMLB-UHFFFAOYSA-N 0.000 description 2
- AXQXKWOXIMDIPN-UHFFFAOYSA-N 3-decyl-2-thiophen-2-ylthiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1CCCCCCCCCC AXQXKWOXIMDIPN-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- 238000006619 Stille reaction Methods 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GGRLKHMFMUXIOG-UHFFFAOYSA-M 2-acetyloxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC(=O)OCC[N+](C)(C)C GGRLKHMFMUXIOG-UHFFFAOYSA-M 0.000 description 1
- RTMOGLNIQKNIAH-UHFFFAOYSA-N 5,6-dimethylthieno[3,2-b]thiophene Chemical compound C1=CSC2=C1SC(C)=C2C RTMOGLNIQKNIAH-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101000610640 Homo sapiens U4/U6 small nuclear ribonucleoprotein Prp3 Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019800 NbF 5 Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 101001110823 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L6-A Proteins 0.000 description 1
- 101000712176 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L6-B Proteins 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 102100040374 U4/U6 small nuclear ribonucleoprotein Prp3 Human genes 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- ZZQWYVKWJHBWRC-UHFFFAOYSA-N [O].C(CCCCCCCCCCC)OCCCCCCCCCCCCC Chemical compound [O].C(CCCCCCCCCCC)OCCCCCCCCCCCCC ZZQWYVKWJHBWRC-UHFFFAOYSA-N 0.000 description 1
- YSNYZCPALUKLFL-UHFFFAOYSA-N [O].CCCCCCCCCCC Chemical compound [O].CCCCCCCCCCC YSNYZCPALUKLFL-UHFFFAOYSA-N 0.000 description 1
- LXLLRHLKPYGEJC-UHFFFAOYSA-N [O].O(CCCCC)C(CCCCCC)OCCCCCC Chemical compound [O].O(CCCCC)C(CCCCCC)OCCCCCC LXLLRHLKPYGEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GCUVBACNBHGZRS-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopenta-2,4-dien-1-yl(diphenyl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.c1cc[c-](c1)P(c1ccccc1)c1ccccc1 GCUVBACNBHGZRS-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OTIVLGJBKUFOEX-UHFFFAOYSA-N n-tetradecoxyaniline Chemical compound CCCCCCCCCCCCCCONC1=CC=CC=C1 OTIVLGJBKUFOEX-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
- C07D333/10—Thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D345/00—Heterocyclic compounds containing rings having selenium or tellurium atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Thin Film Transistor (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Semiconductor Memories (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to novel mono-, oligo- and polythieno[3,2-b]thiophenes, to their use as semiconductors or charge transport materials, in optical, electro-optical or electronic devices like for example liquid crystal displays, optical films, organic field effect transistors (FET or OFET) for thin film transistor liquid crystal displays and integrated circuit devices such as RFID tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices, and to field effect transistors, light emitting devices or ID tags comprising the novel polymers.
Description
Technical field
The present invention relates to also [3,2-b] thiophene of novel monomeric, oligomeric and Polythiophene.The invention further relates to them as semi-conductor or charge transfer material, be used for optics, electrooptics or electron device such as liquid-crystal display, blooming, be used for the organic field effect tube (FET or OFET) of Thin Film Transistor-LCD, and integrated circuit (IC)-components such as RFID label, the electroluminescent device in the flat-panel monitor and the purposes that is used for photovoltaic and sensor component.The invention further relates to the field-effect transistor, luminescent device or the ID label that comprise this new polymers.
Background technology
In the prior art, the polymkeric substance that is made of the multiple thiophene unit has been in the news and has demonstrated in FET uses superperformance as charge transfer material.For example, poly-(3-alkyl) thiophene of regio-regular is verified is that mobility is recorded as one of the highest polymkeric substance people such as (, Science, the 1998,280,1741st page) Sirringhaus up to now.In addition, for example at EP 1 327 646 A1, EP 1 327 647 A1, disclosedly among EP 1 329 474 A1 or EP 1 329475 A1 comprise the different numbers of alkylthrophene and the Polythiophene analogue of regional isomer shows rational carrier mobility.
This characteristic it is believed that owing to two factors.At first, arranging on the polymer backbone that alkyl group side chain allows this polymkeric substance to be organized into ordered structure automatically from solution when applying.This helps to arrange the transition mechanism of charge transfer.Secondly, it is useful to exist sulphur atom to show charge transfer in polymer backbone.Though do not know accurate mechanism, the interaction of the sulphur d-track on adjacent polymer chains helps electric charge transition mechanism by inference.
Yet disclosed polymkeric substance only shows no more than 0.1cm in the above-mentioned prior art document
2V
-1s
-1Carrier mobility.In addition, the material of prior art often only shows limited solubleness, and this is a shortcoming when being used for producing the semiconductor devices as thin film transistor (TFT) or field-effect transistor (FET) when processable polymer.
Therefore, in order to realize transistor characteristic, the charge mobility and the solvability that further strengthen organic polymer are wished.
Summary of the invention
The purpose of this invention is to provide the novel organic materials as semi-conductor or charge transfer material, it synthesizes, has high charge mobility and good workability easily.This material particularly should easily be processed to form the thin and large-area film that is used for semiconducter device.In addition, this material should be oxidation-stabilized, yet keeps or even improve required electric property.
The present inventor has been found that based on thieno-[3,2-b] thiophene (1) material (TT)
R=for example, alkyl
Especially comprise 3, the oligopolymer of the thiophene of dibasic TT group of 6-and/or replacement or the TT of selenophen base and (be total to) polymkeric substance demonstrate the carrier mobility of raising and keep the solution processable performance of hope simultaneously.
The TT material is known in the prior art.For example, people such as Nakayama, Heterocycles has reported 3 for the 1994,38,143rd page, 6-dimethyl TT.People such as Saidman, J.Appl.Electrochemistry has reported 3 for the 2001,31,839th page, the electricity of 6-dimethyl TT causes polymerization, however this only obtains undissolved polymkeric substance.People such as Nakayama, Tetrahedron has reported 3 for the 1996,52,471st page, dipolymer, trimer and the tetramer of 6-dimethyl TT.This tetramer has low-down solubleness equally and does not report electric property.
People such as Fuller, J.Chem.Soc.Perkin Trans.1997,1,3465-70 reported contain alkylthio (S-Me ,-S-Ph) and silyl alkyl (Si (Me)
3) substituent 3, the dibasic TT of 6-.Yet, polymkeric substance is not disclosed.In addition, thioether often is undesirable, because the electron rich of these side chains can produce the unsettled polymkeric substance in oxidation aspect.
Some reports that the polymkeric substance that contains unsubstituted TT is also arranged in the prior art.People such as Kossmehl, Makromol.Chem.1982 has reported for 183, the 2747 pages to contain for example co-polymer of the TT of vinylidene connection base.Yet these polymkeric substance are poorly soluble and do not report their electrical characterization.People such as Rutherford, Macromolecules has reported for the 1992,125,2294th page to contain that synthetic and electricity that alkynyl connects the TT of base causes that polymeric does not replace or the TT of monomethylation synthetic.All these polymkeric substance are insoluble equally.
WO99/12989 discloses the oligopolymer and the polymkeric substance that will comprise two or more fused thiophene rings and has been used for TFT and FET, and these thiphene ring can be replacements or unsubstituted.Yet, do not carry out open particularly to (being total to) polymkeric substance or their preparation with dibasic TT.
Therefore, another object of the present invention provides thieno-[3,2-b] thiophene (TT) material, it is compared in the manufacturing of semiconducter device with the TT material of prior art and can more easily process, have higher stability and also allow more easily synthetic on a large scale.
Find that above-mentioned purpose can realize by providing according to monomer of the present invention, oligopolymer and (being total to) polymkeric substance.
Summary of the invention
The present invention relates to comprise at least one thieno-[3,2-b] thiophene-2, monomer, oligopolymer and the polymkeric substance of 5-two bases (TT) group, it is characterized in that they comprise at least one at the substituted TT group of 3-and 6-position and/or at least one is at 3-and/or 4-position substituted thiophene-2,5-two bases or selenophen-2,5-two groups.
The invention further relates to the semi-conductor or charge transfer material, element or the device that comprise at least a monomer as defined above, oligopolymer or polymkeric substance.
The invention further relates to purposes according to polymkeric substance of the present invention, as charge transfer, characteristic of semiconductor, conduction, photoconductivity or luminescent material are used for optics, electrooptics or electronic component or device, organic field effect tube (OFET), unicircuit (IC), thin film transistor (TFT), flat-panel monitor, RF identification (RFID) label, electroluminescent or photo luminescent devices or element, Organic Light Emitting Diode (OLED), the backlight of indicating meter, photovoltaic or sensor component, electric charge injection layer, schottky diode, complanation layer, antistatic film, conductive substrate or pattern, electrode materials in the battery, photo-conductor, electrofax is used, electrophotographic recording, organic memory device, both alignment layers, the purposes in makeup or the pharmaceutical composition, or be used to detect and differentiate the purposes of dna sequence dna.
The invention further relates to optics, electrooptics or the electron device, FET, unicircuit (IC), TFT, OLED or the both alignment layers that comprise according to characteristic of semiconductor of the present invention or charge transfer material, element or device.
The invention further relates to the TFT or the tft array that comprise according to semi-conductor of the present invention or charge transfer material, element or device or FET, IC, TFT or OLED, it is used for flat-panel monitor, RF identification (RFID) label, electroluminescent display or backlight.
The invention further relates to the safety label or the device that comprise according to FET of the present invention or RFID label.
Detailed Description Of The Invention
Especially can be used as the charge transfer semi-conductor according to monomer of the present invention, oligopolymer and polymkeric substance, because they have high carrier mobility.A this improved reason of carrier mobility aspect except the sulphur atom concentration of per unit length Nei Genggao, is the enhanced planeness and the conjugation degree of condensed ring system.For example, have three two keys and two sulphur atoms in each molecule of TT, and have two two keys and a sulphur atom in each molecule of thiophene, 2, have four two keys and two sulphur atoms in each molecule of 2-bithiophene (bithiophene).
TT and functionalized aromatics or the copolymerization of unsaturated comonomer can further improve solvability and charge transport properties.The variation of aromatic monomer provides the method for cutting out of the band gap of polymkeric substance.Obtain better stability and higher carrier mobility like this.
The compound according to the present invention that comprises dibasic TT group is especially preferred.Unsubstituted TT direct polymerization is often produced insoluble polymkeric substance, and therefore they should carry out polymerization so that the polymkeric substance with good solubility to be provided with the comonomer that has solubilization radical.Can directly provide soluble polymer, yet particularly under the homopolymer situation, the substituting group orientation on each TT must be carefully controlled to guarantee high degree of regioregularity according to the TT of adjacent replacement with mono-substituted TT polymerization.It is necessary that high degree of regioregularity has been presented under the situation of mono-substituted thiophene the material with good carrier mobility is provided.Yet the synthetic of height regio-regular material is synthetic extra complicacy and the expense brought abnormal and that can give this base polymer.
Wherein the TT group is especially preferred by the polymkeric substance of two alkyl or fluoro-alkyl replacement.Fluoro-alkyl and alkyl group side chain are introduced the solvability of having improved them in the TT group and therefore improved their solution processable.In addition, the existence of fluoro-alkyl side chain also makes these materials can be effectively as the n-N-type semiconductorN.The substituent electrophilic characteristic of fluoro-alkyl also will reduce HOMO further and obtain more stable material, and this material is more insensitive to oxygenizement.
The compound of general formula I is especially preferred:
-([A]
a-[B]
b-[C]
c-[D]
d)
n- I
Wherein
A and C are independently of one another:
B and D are-CX independently of one another
1=CX
2-,-C ≡ C-or optional by one or more radicals R
1The arylidene or the heteroarylidene that replace,
R
1And R
2Represent H independently of one another; Halogen; Optional substituted aryl or heteroaryl; Or contain straight chain, branching or the cyclic alkyl of 1 to 20 C atom, and they can be unsubstituted, are replaced or polysubstituted by F, Cl, Br, I or CN are single, and wherein one or more non-conterminous CH
2Group randomly in each case independently of one another by-O-,-S-,-NH-,-NR
0-,-SiR
0R
00-,-CO-,-COO-,-OCO-,-O-CO-O-,-S-CO-,-CO-S-,-CX
1=CX
2-or-C ≡ C-substitutes and satisfies O and/or the S atom does not directly connect each other,
X
1And X
2Be H, F, Cl or CN independently of one another,
R
0And R
00Be H independently of one another, contain the alkyl of 1 to 12 C atom, or aryl,
A and c are 0 or 1 independently of one another, wherein at least one group [(A)
a-(B)
b-(C)
c(D)
d] in, a and/or c are 1,
B and d are 0,1 or 2 independently of one another,
N is 〉=1, and preferred 1 to 10,000 integer,
Wherein under the situation of n＞1, group [(A)
a-(B)
b-(C)
c-(D)
d] can be identical or different, and condition is
A) this compound comprises at least one by radicals R
1And R
2The group A or the C that replace, this radicals R
1And R
2Have at least 3 C atoms separately,
And/or
B) this compound comprises at least one group B or D, and this B or D are the radicals R that 3-and/or 4-position are different from H
1The thiophene-2 that replaces, 5-two bases or selenophen-2,5-two bases.
The compound of general formula I is preferably selected from the compound of general formula I 1
R
3-[(A)
a-(B)
b-(C)
c-(D)
d]
n-R
4 I1
R wherein
1, R
2, a, b, c, d and n have one of implication of general formula I independently of one another,
R
3And R
4Be H independently of one another, halogen, C
1-C
12Alkyl, Sn (R
0)
3, B (OR
0)
2, CH
2Cl, COH, CH=CH
2, SiR
0R
00R
000, or optional aryl or the heteroaryl that replaces,
R
000Have and be R in the general formula I
00One of implication that provides and
R
0And R
00Implication with general formula I.
R
3And R
4Be also referred to as " end group " hereinafter.
Has identical repeating unit [(A)
a-(B)
b-(C)
c-(D)
d] general formula I and oligopolymer and the polymkeric substance of I1 (promptly wherein n＞1) be especially preferred.
R wherein
1And R
2For the compound of the general formula I of identical group and I1 is further preferred.
Oligopolymer and polymkeric substance are especially preferred, those of general formula I and I1 especially, and they have 2 to 5000, and especially 10 to 5000,20 to 1000 the polymerization degree (n in the general formula I) very preferably.
Oligopolymer and polymkeric substance are further preferred, those of general formula I and I1 especially, and they have 5000 to 300,000, especially 10,000 to 100,000 molecular weight.
In oligopolymer of the present invention and polymkeric substance, group [(A)
a-(B)
b-(C)
c-(D)
d] can be independently from each other the group of general formula I, thus oligopolymer or polymkeric substance can comprise identical or different repeating unit [(A)
a-(B)
b-(C)
c-(D)
d].Therefore this oligopolymer and polymkeric substance comprise homopolymer and multipolymer, for example
Random multipolymer on the-statistics, for example contain sequence monomer such as A-B-B-C-B-D-A-B-D-or-multipolymer of A-C-A-A-C-,
-alternating copolymer, for example contain sequence monomer as-A-B-A-B-A-B-A-B-,-A-B-C-A-B-C-or-multipolymer of A-B-C-D-A-B-C-D, they also can be regarded as is respectively monomeric unit (A-B), (A-B-C) and homopolymer (A-B-C-D), or contain sequence monomer as-(A-B-C)-(A-B)-(A-B-C)-(A-B)-multipolymer and
-segmented copolymer, for example contain sequence monomer as-A-A-B-B-B-B-C-C-C-D-D-D-(if A, B, C and D are considered to be monomeric unit) or contain sequence monomer as-(A-B)-(A-B)-(A-B)-(A-B-C)-(A-B-C)-(A-B-C)-(A-B-C) (if, for example, (A-B) and (A-B-C) be considered to be monomeric unit) multipolymer
Wherein group A, B, C and D preferably form conjugated system together, and wherein occur in addition can being same to each other or different to each other more than once group (for example each group B among sequence-B-B-B-B-B-).
The general formula (A-B) that constitutes by identical repeating unit
n, (A-B-C)
n, (A-B-D)
n, (A-C-D)
n, (B-C-D)
nOr (A-B-C-D)
nPolymkeric substance be especially preferred.
Preferably, group A, B, C and D form conjugated system together.
The regio-regular polymkeric substance of general formula I and I1 is further preferred, the polymkeric substance that especially has the degree of regioregularity of high head-tail (HT) connection.
Degree of regioregularity in these polymkeric substance preferably is 90% at least, especially 95% or higher, very preferably 98% or higher, very preferably 99% to 100%.
The polymkeric substance of regio-regular is favourable, because they show that strong interchain π-π piles up interaction and high degree of crystallinity, this makes them become the charge transfer material that effectively has high carrier mobility.
The polymkeric substance that comprises symmetrical repeating unit is further preferred, and is especially symmetric 3, the dibasic TT-2 of 6-, and 5-two basic monomeric homopolymer, wherein degree of regioregularity is not a problem.
The monomer of general formula I and I1, oligopolymer and polymkeric substance are further preferred, wherein
-b be 1 and B optional be different from the radicals R of H by one or two
1The thiophene-2 that replaces, 5-two bases or selenophen-2,5-two bases,
-R
1And R
2Be selected from the optional C that is replaced by one or more fluorine atoms
3-C
20Alkyl, C
3-C
20Alkenyl, C
3-C
20Alkynyl, C
3-C
20Ester, C
3-C
20Amino, C
3-C
20Fluoro-alkyl and optional aryl or the heteroaryl that replaces, very preferably C
3-C
20Alkyl or C
3-C
20Fluoro-alkyl,
-R
3And R
4Be selected from H, C
1-C
12Alkyl, halogen, Sn (R
0)
3, B (OR
0)
2CH
2Cl, CH
2OH, CH=CH
2, SiR
0R
00R
000With optional aryl or the heteroaryl that replaces,
-P
*Be-OH or-O-Si-R
0R
00R
000, preferred R wherein
0, R
00And R
000For being selected from aryl or C
1-12Alkyl, preferred C
1-C
6The identical or different group of alkyl such as methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl,
-n＞1。
If B or D are arylidene or heteroarylidene, then it preferably contains the single, double or three cyclophane family or the heteroaromatic group of 25 C atoms of as many as, wherein ring can be a condensed, and wherein this heteroaromatic group comprises at least one ring hetero atom, is preferably selected from N, O and S.It is randomly by the one or more replacements among F, Cl, Br, I, the CN; With the straight chain, branching or the cyclic alkyl that contain 1 to 20 C atom, it is unsubstituted, by F, Cl, Br, I ,-CN or-OH is single to be replaced or polysubstituted, and wherein one or more non-conterminous CH
2Group randomly in each case independently of one another by-O-,-S-,-NH-,-NR
0-,-SiR
0R
00-,-CO-, COO-, OCO-,-OCO-O ,-S-CO-,-CO-S-,-CH=CH-or-C ≡ C-substitutes and satisfies O and/or the S atom does not directly connect each other.
Preferred arylidene or heteroarylidene group are selected from: phenylene, wherein one or more CH groups can be substituted by N in addition, or naphthalene, alkyl fluorenes or azoles, thiophene, selenophen, two thienothiophenes, wherein all these groups are randomly by L is single or polysubstituted as defined above.
Especially preferred arylidene or heteroarylidene group are 1,4-phenylene, fluorizated 1,4-phenylene, 2,5-pyridine, 2,5-pyrimidine, p, p '-xenyl, naphthalene-2,6-two bases, thiophene-2,5-two bases, selenophen-2,5-two bases, fluoridize or alkylating thiophene-2 5-two bases or selenophen-2,5-two bases, 2,2 '-two thiophene are fluoridized or alkylating 2,2 '-two thiophene, fluoridize benzo [1,2-b:4,5-b '] two thiophene, 2,5-thiazole, 2, the 5-thiadiazoles, 2,5- azoles and 2,5- diazole, all these groups are not substituted, or by L is single or polysubstituted as defined above.
If R
1-4One of be aryl or heteroaryl, then it preferably contains the single, double or three cyclophane family or the heteroaromatic group of 25 C atoms of as many as, wherein this ring can be a condensed, and wherein this heteroaromatic group comprises at least one ring hetero atom, it is preferably selected from N, O and S.It is randomly by the one or more replacements among F, Cl, Br, I, the CN; With the straight chain, branching or the cyclic alkyl that contain 1 to 20 C atom, it can be unsubstituted, by F, Cl, Br, I ,-CN or-OH is single to be replaced or polysubstituted, and wherein one or more non-conterminous CH
2Group optional in each case independently of one another by-O-,-S-,-NH-,-NR
0-,-SiR
0R
00-,-CO-,-COO-, OCO-,-OCO-O ,-S-CO-,-CO-S-,-CH=CH-or-C ≡ C-substitutes and satisfies O and/or the S atom does not directly connect each other.
Especially preferred aryl and heteroaryl groups are phenyl, fluorizated phenyl, pyridine, pyrimidine, xenyl, naphthalene, thiophene, selenophen, fluorizated thiophene, benzo [1,2-b:4,5-b '] two thiophene, thiazole and azoles, all these groups are unsubstituted, by L is single or polysubstituted as defined above.
If R
1-4One of be alkyl or alkoxyl group (promptly wherein terminal CH
2Group quilt-O-substitutes), then this can be straight chain or branching.It is straight chain preferably, have 3 to 8 carbon atoms and therefore preference propyl group, butyl, amyl group, hexyl, heptyl, octyl group, propoxy-, butoxy in this way, pentyloxy, hexyloxy, heptan oxygen base or octyloxy, in addition nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tridecane oxygen base or tetradecyloxyaniline.
Fluoro-alkyl or fluorinated alkyl or alkoxyl group be straight chain (O) C preferably
iF
2i+1, wherein i is 1 to 20, especially 3 to 15 integer, very preferably (O) C
3F
7, (O) C
4F
9, (O) C
5F
11, (O) C
6F
13, (O) C
7F
15Or (O) C
8F
17, (O) C most preferably
6F
13
CX
1=CX
2Preferably-CH=CH-,-CH=CF-,-CF=CH-,-CF=CF-,-CH=C (CN)-or-C (CN)=CH-.
Halogen is F, Br or Cl preferably.
Heteroatoms is preferably selected from N, O and S.
Wherein-[(A)
a-(B)
b-(C)
c-(D)
d]
n-be selected from the general formula I of following general formula and the compound of I1 is especially preferred:
Wherein, implication one of and the R of n with general formula I has the R that provides in the general formula I
1One of implication or one of the preferred meaning that provides of context, and preferably be different from H.
The monomer, oligopolymer and the polymkeric substance that comprise dibasic TT group and optional thieno-[2, the 3-b] thienyl group that replaces as following general formula those, are more not preferred:
Wherein, R
1And R
2Has one of implication of the general formula I that is different from H, R
5And R
6Has R as defined above
1One of implication.
Compound of the present invention can or be similar to these methods according to currently known methods or following method and synthesize.Further method can obtain from embodiment.
The A part: 3,6-dialkyl group-thieno-[3,2-b] thiophene synthetic:
Remove 3, outside the 6-dimethyl, 3, the preparation of the TT of 6-dialkyl groupization is not also reported in the prior art.Shown in the following synoptic diagram 13, the one still process operation steps of 6-dimethyl thieno-[3,2-b] thiophene, are reported in the 143rd page at Heterocycles 1994,38 by people such as Nakayama.Yet the shortcoming of this method is, because closed loop mechanism, it can not stand the check of preparation than long-chain alkyl derivative.Yet,, wish than the introducing of long alkyl chain for the polymkeric substance of solution processable is provided.
Synoptic diagram 1: the preparation (prior art) of dimethyl-thieno-[3,2-b] thiophene
As thieno-[3, the 2-b] thiophene (1) in synoptic diagram 2, described (R=H) synthesize Trans.1997 at people's such as Fuller J.Chem.Soc.Perkin, 1, report among the 3465-70.Same reference has also been reported by thieno-[3,2-b] thiophene being examined tetrabormated and has also been gone back original preparation 3, the operation steps of 6-two bromo thieno-s [3,2-b] thiophene (2), as illustrate shown in Figure 3.By lithiumation with react with Electron Affinities disulphide subsequently two bromo intermediates (2) are changed into alkylthio (SR) derivative.Yet thioether is undesirable in this case, because the electron rich characteristic of these side chains can produce the unsettled polymkeric substance in oxidation aspect.In addition, long-chain alkyl derivative can not be introduced by similar path, and this is owing to the low reactivity of alkyl halide, and it stops reaction at low temperatures.Be higher than under-78 ℃ the temperature dilithium salt open loop of (2) (referring to people's such as Fuller J.Chem.Soc.Perkin Trans.1999,1, the 1273 page) and produce the product of non-condensed.
Synoptic diagram 2: synthetic (prior art) of thieno-[3,2-b] thiophene
Synoptic diagram 3: by two bromo intermediate preparation 3,6-dialkyl group thienothiophene (prior art)
According to of the present invention 3, exemplary description has been carried out in preferably synthesizing of 6-dialkyl group thieno-[3,2-b] thiophene in synoptic diagram 4, these synthetic two bromo intermediates (2) that use.Find, at bidentate type palladium catalyst (Pd (dppf) Cl for example
2) existence under cross coupling productive rate with excellence under microwave heating of (2) and organic zinc reactant take place.Therefore in THF, heat octyl group zinc bromide, 3,6-two bromo thieno-s [3,2-b] thiophene and Pd (dppf) Cl down at 140 ℃
2Obtained productive rate in 7 minutes and be 95% 3,6-dioctyl thieno-[3,2-b] thiophene.
Synoptic diagram 4
B part: comprise 3, the polymkeric substance of 6-dialkyl group thienothiophene
Cause polymerization process by electricity and make 3, also [3,2-b] the thiophene polymerization and obtain insoluble polymkeric substance (J.Appl.Electrochemistry of 6-thioxene; 2001; 31, the 839 pages).Yet such polymkeric substance is not suitable for according to application of the present invention.
People such as Nakayama (Tetrahedron, the 1996,52,471st page) have described 3, and the 6-thioxene is dipolymer, trimer and the tetramer of [3,2-b] thiophene also.This tetramer has low-down solubleness equally and does not report electric property.
According to the present invention, 3, the homopolymer (3) of 6-dioctyl thieno-[3,2-b] thiophene and multipolymer are preferably as illustrating shown in Figure 5 the preparation.Such polymkeric substance height dissolves in organic solvent and can easily be processed into film.
Synoptic diagram 5
C part: the polymkeric substance that comprises unsubstituted thieno-[3,2-b] thiophene
Have some reports about the polymkeric substance that comprises unsubstituted TT.People such as Kossmehl are at Makromol.Chem.1982, have reported in 183, the 2747 to have the multipolymer (4) that vinylidene connects the TT of base.Yet such polymkeric substance is poorly soluble and does not report their electrical characterization.
People such as Rutherford are at Macromolecules, have reported that having alkynyl connects TT (5) synthetic of base and make unsubstituted TT electricity cause polymerization and obtain (6) in the 1992,125,2294th page.All these polymkeric substance are insoluble equally.
One aspect of the present invention is the multipolymer of preparation unsubstituted thieno-[3,2-b] thiophene and alkylation thiophene.This base polymer is soluble in organic solvent, and alkyl group side chain can easily be piled up so that closelypacked structure to be provided.This class formation is of value to charge transfer.Polymkeric substance (7) can be by easily synthetic as signal Stille coupling shown in Figure 6.The Stille coupling before had been used for preparing conjugated polymers (referring to people such as Babudri, J.Mater.Chem., 2004,14,11-34 page or leaf).
Synoptic diagram 6
Polymkeric substance (7) shows good transistor characteristic, and wherein carrier mobility (μ) is 0.02cm
2/ vs (not optimizing).
Another aspect of the present invention relates to according to the oxidation of compound of the present invention and material and reduction form.The losses or gains electronics causes the formation of height delocalized ionic species, and this ionic species has high conductivity.This may take place when touching common dopants.The doping agent and the adulterating method that are fit to are well known by persons skilled in the art, for example, from EP 0 528 662, US5,198,153 or WO 96/21659 know.
Adulterating method must be included in usually in the redox reaction and handle semiconductor material and form delocalized ion center in this material with oxidation or reductive agent, and wherein Dui Ying counter ion are derived from applied doping agent.The adulterating method that is fit to comprises: for example be exposed to doping steam under normal pressure or decompression, the electrochemical doping in comprising the solution of doping agent makes doping agent contact with the semiconductor material for the treatment of thermodiffusion and doping agent is carried out ion implantation in semiconductor material.
When electronics was used as current carrier, suitable doping agent for example was halogen (for example, I
2, Cl
2, Br
2, ICl, ICl
3, IBr and IF), Lewis acid (for example, PF
5, AsF
5, SbF
5, BF
3, BCl
3, SbCl
5, BBr
3And SO
3), protonic acid, organic acid or amino acid (for example, HF, HCl, HNO
3, H
2SO
4, HClO
4, FSO
3H and ClSO
3H), transistion metal compound (for example, FeCl
3, FeOCl, Fe (ClO
4)
3, Fe (4-CH
3C
6H
4SO
3)
3, TiCl
4, ZrCl
4, HfCl
4, NbF
5, NbCl
5, TaCl
5, MoF
5, MoCl
5, WF
5, WCl
6, UF
6And LnCl
3(wherein Ln is a lanthanon), negatively charged ion (for example, Cl
-, Br
-, I
-, I
3 -, HSO
4 -, SO
4 2-, NO
3 -, ClO
4 -, BF
4 -, PF
6 -, AsF
6 -, SbF
6 -, FeCl
4 -, Fe (CN)
6 3-, the negatively charged ion of various sulfonic acid, for example aryl-SO
3 -).When the hole was used as current carrier, the example of doping agent was positively charged ion (for example, H
+, Li
+, Na
+, K
+, Rb
+And Cs
+), basic metal (for example, Li, Na, K, Rb and Cs), alkaline-earth metal (for example, Ca, Sr and Ba), O
2, XeOF
4, (NO
2 +) (SbF
6 -), (NO
2 +) (SbCl
6 -), (NO
2 +) (BF
4 -), AgClO
4, H
2IrCl
6, La (NO
3)
36H
2O, FSO
2OOSO
2F, Eu, vagusstoff, R
4N
+, (R is an alkyl), R
4P
+(R is an alkyl), R
6As
+(R is an alkyl) and R
3S
+(R is an alkyl).
The conduction form of compound of the present invention and material can be used as organic " metal " in application, for example, but be not limited to, electric charge injection layer and ITO complanation layer in Organic Light Emitting Diode is used, the film of flat-panel monitor and touch-screen, antistatic film, through the conductive substrate of printing, pattern or the beam trace in printed circuit board (PCB) and the electrical condenser for example in the electronic application.
A preferred embodiment of the present invention is related to the general formula I of mesomorphic (mesogenic) or liquid crystal and monomer, oligopolymer and the polymkeric substance of preferred sub-general formula thereof.These materials especially can be used as semi-conductor or charge transfer material, because can they be arranged in the orientation of the high-sequential of homogeneous in its mesomorphic phase by known technology, thereby show the higher degree of order that causes extra high carrier mobility.
In order to induce or to strengthen the mesomorphic phase behavior, also may make according to monomer of the present invention, oligopolymer and polymkeric substance and other is from mesomorphic or liquid crystal monomer copolymerization well known in the prior art.
Liquid crystal material with nematic phase and/or smectic phase is especially preferred.Use for FET, the smectic type material is especially preferred.Use for OLED, nematic or smectic type material are especially preferred.Smectic type A (S
A) phase, the smectic phase of high-sequential such as S in addition
B, S
E, S
GAnd S
FBe especially preferred mutually.
Aligning of liquid crystal material can for example realize in the following manner: the base material that this material is coated on it is handled, in coating procedure or afterwards, this material is sheared, the material that has applied is applied magnetic field or electric field, perhaps surface active cpd is added in this material.The summary that aligns technology (is edited John Wiley ﹠amp by for example I.Sage at " Thermotropic LiquidCrystals " by G.W.Gray; Sons), in 1987, the 75-77 pages or leaves, with by T.Uchida and H.Seki " Liquid Crystals-Applications andUses Vol.3 " (editing) by B.Bahadur, World Scientific Publishing provides in Singapore's 1992, the 1-63 pages or leaves.The summary that aligns material and technology is by J.Cognard, Mol.Cryst.Liq.Cryst.78, and supplementary issue 1 (1981), the 1-77 page or leaf provides.
Can also comprise one or more other component of being fit to according to monomer of the present invention, oligopolymer and polymkeric substance, for example catalyzer, sensitizing agent, stablizer, stopper, chain-transfer agent, coreaction monomer, surface active cpd, lubricant, wetting agent, dispersion agent, hydrophobizing agent, tackiness agent, FLOW IMPROVERS, defoamer, air release agent, thinner, reactive diluent, auxiliary agent, tinting material dye or pigment.
Monomer of the present invention, oligopolymer and polymkeric substance can be used as optics, electronics and semiconductor material, especially can be used as the charge transfer material in the field-effect transistor (FET), for example the element of using as unicircuit, ID label or TFT.Perhaps, they can be used for the Organic Light Emitting Diode (OLED) of electroluminescent display applications or as for example backlight liquid crystal display lamp, as photovoltaic or sensor material, be used for electrophotographic recording, and be used for other semiconductor application.
Especially, show favourable solubility property according to oligopolymer of the present invention and polymkeric substance, this solubility property allows the preparation method of the solution of these compounds of use.Therefore, film (comprising layer and coating) can be by low-cost technology of preparing, and for example spin coating produces.The solvent or the solvent mixture that are fit to comprise alkane and/or aromatic substance, especially their fluorinated derivatives.
Material of the present invention can be used as optics, electronics and semiconductor material, especially as the charge transfer material in the field-effect transistor (FET), as photovoltaic or sensor material, is used for electrophotographic recording, and is used for other semiconductor application.This type of wherein organic semiconductor material be known as the FET of arranged in form between gate-dielectric and drain electrode and source electrode of film, for example from US 5,892,244, WO 00/79617, US 5,998,804 and the reference in the background technology chapters and sections, quoted and below know in the reference enumerated.Because these advantages, as using according to the low cost preparation of the solubility property of compound of the present invention and the big surperficial workability that therefore has, the advantageous applications of these FET is for example unicircuit, TFT indicating meter and security application.
In security application, field-effect transistor and other contain the device of semiconductor material, as transistor or diode, can be used for ID label or safety label identifies and prevents to counterfeit valuable securities as bank note, credit card or ID card, national ID file, license licensed licenser licence or any product with monetary value, as stamp, admission ticket, stock, check etc.
Perhaps, can be used for organic luminescent device or diode (OLED), for example be used for display application or be used as for example backlight liquid crystal display lamp according to monomer of the present invention, oligopolymer and polymkeric substance.Common OLED uses multilayered structure to realize.Emission layer is clipped between one or more electron transfer layers and/or the hole transmission layer usually.By applying voltage, move to emission layer as current carrier in electronics and hole, and their recombine causes exciting and therefore makes the lumophore unit that is included in this emission layer luminous in this emission layer.Compound of the present invention, material and film can be used among charge transport layer one or more and/or be used for emission layer, corresponding to their electricity and/or optical property.In addition, if show electroluminescent properties or comprise electroluminescent group or compound that according to compound of the present invention, material and film itself then they are especially favourable in the use of emission layer inside.The monomer, selection, sign and the processing oligomeric and polymerizable compound or material that are fit to that are used for OLED are well known to a person skilled in the art, for example referring to Meerholz, Synthetic Materials, 111-112,2000,31-34, Alcala, J.Appl.Phys., 88,2000,7124-7128 and the document of wherein quoting.
According to another kind of purposes, compound of the present invention, material or film, especially those of display light electroluminescent properties, can be used as source material, as in EP 0 889 350 A1 or people such as C.Weder at Science, 279,1998, the source material of the display device of those that describe among the 835-837.
According to another kind of purposes, compound of the present invention, material or film can be individually or are used from other material one or as the both alignment layers in LCD or the OLED device, as described in the US2003/0021913.Can improve the specific conductivity of both alignment layers according to the use of charge transport compound of the present invention.When being used for LCD, the specific conductivity of this raising can be reduced in the disadvantageous residual dc effect in the changeable LCD unit (cell) and suppress that image keeps or, for example in ferroelectric LCD, reduce the residual charge that produces owing to the spontaneous polarization electric charge that switches ferroelectric LC.When being used for comprising the OLED device of the luminescent material that is provided on the both alignment layers, the specific conductivity of this raising can strengthen the electroluminescent of this luminescent material.Have the compound of mesomorphic or liquid crystal property or an anisotropic membrane that material can form above-mentioned orientation according to of the present invention, they especially can be used as both alignment layers to induce or to strengthen aligning in the liquid crystal media that is provided on the described anisotropic membrane.Material according to the invention also can combine with compound that can photic isomery and/or chromophore to be used for or as the photic layer that aligns, described in US 2003/0021913.
According to another kind of purposes, material according to the invention and polymkeric substance, especially their soluble derivative (derivative that for example contains polarity or ionic side group) or the adulterated form of ionic means can be used as chemical sensor or material to detect and to differentiate dna sequence dna.These purposes for example are described in L.Chen, D.W.McBranch, H.Wang, R.Helgeson, F.Wudl and D.G.Whitten, Proc.Natl.Acad.Sci.U.S.A.1999,96,12287; D.Wang, X.Gong, P.S.Heeger, F.Rininsland, G.C.Bazan and A.J.Heeger, Proc.Natl.Acad.Sci.U.S.A.2002,99,49; N.DiCesare, M.R.Pinot, K.S.Schanze and J.R.Lakowicz, Langmuir 2002,18, and 7785; D.T.McQuade, A.E.Pullen, T.M.Swager, Chem.Rev.2000,100,2537.
Also can be used for makeup or pharmaceutical composition according to polymkeric substance of the present invention and material, for example as the disclosed make-up composition that is used for hair treatment among EP 1 498 112 A2.
Embodiment
Following examples are used to illustrate the present invention without limitation.In context, except as otherwise noted, all temperature are degree centigrade to provide, and all per-cent is weight percent.Unless otherwise, all being reflected under the nitrogen atmosphere carried out.Change mutually by the blending means of DSC and optical microscopy and determine.S
xAnd S
X1Be meant that the smectic phase of deterministic nature does not change.
Embodiment 1
3 as described below preparations of polymkeric substance:
Poly-(3,6-dioctyl thieno-[3,2-b] thiophene) (3):
Under nitrogen, with anhydrous FeCl
3(0.71g 4.39mmol) adds in the three-necked flask.Add anhydrous chloroform (20mL) and produce suspension.With 3, (0.40g, 1.10mmol) solution in anhydrous chloroform (20mL) adds this FeCl to 6-dioctyl thieno-[3,2-b] thiophene
3In the suspension.Under RT, stirred this reaction mixture 24 hours, make nitrogen bubble by this mixture to remove formed HCl.This reaction mixture is poured in the methyl alcohol (200mL).Leach sedimentary polymkeric substance and use methanol wash.Stir this polymkeric substance 24 hours in the ammonia solution 25% (60mL) with this polymkeric substance dedoping thing.Leach this polymkeric substance, and wash with water, then use methanol wash.Respectively extracted this polymkeric substance 24 hours with methyl alcohol (soxhlet extraction (soxhlet)) with acetone (soxhlet extraction).At last this polymkeric substance is dissolved in the warm chloroform, filtration also precipitates in methyl alcohol.Collect this polymkeric substance and the dry 29mg product that produces under vacuum by centrifugation.GPC(CHCl
3)Mn(8,000g/mol)，Mw(52,400g/mol)。λ
Max348nm (solid film).
1H NMR is the same as expected.
Embodiment 2
Polymkeric substance 7 is by following described the preparation:
2, two trimethylammonium stannyl thieno-[3, the 2-b] thiophene of 5-:
With thieno-[3,2-b] thiophene (referring to people's such as Fuller J.Chem.Soc.PerkinTrans.1997,1,3465-70) (2.00g, solution 14mmol) are dissolved in and are cooled to-78 ℃ among the anhydrous THF (100ml) and under nitrogen.(12ml, the hexane solution of 2.5M 30mmol), and allow gained solution be warming to 20 ℃ and stirred 3 hours in 30 minutes under this temperature to drip the solution of n-Butyl Lithium in 5 minutes.Gained suspension is cooled to-78 ℃, and add immediately trimethyltin chloride as solid form (5.9g, 30mmol).Allow be reflected at and be warming to RT in 4 hours and restir 20 hours under this temperature.By adding saturated sodium bicarbonate (100ml) with reaction terminating.Add ethyl acetate (50ml), and each layer separated.With yellow soda ash (the 2M aqueous solution of 80ml) and salt solution (80ml) washing organic layer, dry (sodium sulfate) filters and under reduced pressure concentrates.Install to the crude product of gained on the anti-phase silica column of 20g dryly and use the acetonitrile wash-out.Collect fraction just, concentrate and recrystallization and obtain the product of white flakes form from acetonitrile.M/Z cluster center is at 466 (M
+).Find C, 30.9; H, 4.4.C
12H
20S
2Sn
2Calculated value be C, 30.9; H, 4.3.
1H NMR(300MHz，CDCl
3)δ7.26(s，2H)，0.39(s，18H)。
13C NMR(75MHz，CDCl
3)δ147.5，141.2，126.1，-8.2。
5,5 '-two bromos-4,4 '-two (decyl)-2,2 '-bithiophene:
Be similar to working method (referring to M.Zagorska and B.Krische, Polymer, the 1990,31,1379th page) preparation 4,4 published '-two (decyl)-2,2 '-bithiophene.
In 1 hour, with N-bromosuccinimide (5.40g, 4,4 under 30mmol) portioning adds in the dark 5 ℃ to '-two (decyl)-2,2 '-(6.60g is 14.8mmol) in the solution in chloroform (100ml) and Glacial acetic acid (100ml) for bithiophene.Make gained solution be warming to 20 ℃ and restir 16 hours.Under reduced pressure except that desolvating and resistates being suspended among the MTBE (200ml).Filtering solution is removed the succinimide by product.Yellow soda ash with 5% (100ml), water (100ml) and salt solution (100ml) wash filtrate, dry (sodium sulfate) filters and under reduced pressure concentrates.By going up reversed-phase column chromatography,, be further purified the crude product of gained with 2: 1 acetonitriles/THF wash-out at RP18 silicon-dioxide (23g).Recrystallization obtains product from ethyl acetate at last.HRMS 602.1248 (C
28H
44S
2Br
79 2Calculated value be 602.1251).
1H NMR (300MHz, CDCl
3) δ 6.77 (s, 2H), 2.70 (t, 4H), 1.57 (quintet, 4H), 1.28 (m, 28H), 0.88 (t, 6H).
13C NMR(75MHz，CDCl
3)δ143.0，136.1，124.5，107.9，31.9，29.62，29.57，29.40，29.35，29.2，22.7，14.2。
Poly-(2, two (3-decylthiophene-2-yl) thieno-[3, the 2-b] thiophene of 5-) (7):
With 5,5 '-two bromos-4,4 '-didecyl bithiophene (182mg, 0.3mmol), 2, two (trimethylammonium the stannyl)-thieno-s [3 of 5-, 2-b] thiophene (140mg, 0.3mmol), four (triphenyl phosphine) palladium (0) (5.0mg, 1.4mol%) and chlorobenzene (4.5ml) add and to be equipped with in the tubular vial of 10ml of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, PersonalChemistry Ltd) and heated 10 minutes to 200 ℃.In case reach this temperature, only calculate elapsed time.After being cooled to RT, reaction mixture being precipitated in the mixture of methyl alcohol (50ml) and concentrated hydrochloric acid (2ml) and and stirring 16 hours down at 20 ℃.Filter out precipitation, and respectively extracted this precipitation 12 hours with methyl alcohol (soxhlet extraction) and acetone (soxhlet extraction).At last this polymkeric substance is dissolved in the warm chlorobenzene, filtration also precipitates in methyl alcohol.Collect this polymkeric substance and the dry 92mg product that obtains under vacuum by centrifugation.GPC(CHCl
3)Mn(8,750g/mol)，Mw(19,200g/mol)。λ
Max547nm (solid film).
1H NMR (300MHz, CDCl
3, 50 ℃) δ 7.26 (s, 2H), 7.03 (s, 2H), 2.79 (t, 4H), 1.70 (quintet, 4H), 1.4-1.20 (m, 28H), 0.88 (t, 6H).
Embodiment 3
Polymkeric substance 8 is by following described the preparation:
2,5-two bromos-3,4-didecyl thiophene
Be similar to working method (referring to S.Destri, M.Pasini, C.Pelizzi, W.Porzio, G.Predieri, C.Vignali Macromolecules, the 1999,32,353rd page) preparation of having published 3,4-didecyl thiophene.Be similar to the working method published (referring to P.B uerle, F.Pfau, H.Schlupp, F.W ü rthner, K.U.Gaudl, M.B.Caro, P.Fischer J.Chem.Soc., Perkin Trans.2,1993, the 489 pages) by 3,4-didecyl thiophene preparation 2,5-two bromos-3,4-didecyl thiophene.
Poly-(3,4-didecyl thiophene-altogether-thieno-[3,2-b] thiophene) (8):
With 2,5-two bromos-3,4-didecyl thiophene (157mg, 0.3mmol), 2, two (trimethylammonium the stannyl)-thieno-s [3 of 5-, 2-b] thiophene (140mg, 0.3mmol), four (triphenyl phosphine) palladium (0) (5.0mg, 1.4mol%) and chlorobenzene (4.5ml) add and to be equipped with in the tubular vial of 10ml of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, Personal Chemistry Ltd) and heated 10 minutes to 200 ℃.After being cooled to RT, reaction mixture being precipitated in the mixture of methyl alcohol (20ml) and 37% hydrochloric acid (2ml) and and stirring 48 hours down at 20 ℃.Leach polymkeric substance, use methanol wash, and dry under vacuum.With methanol wash polymkeric substance (passing through soxhlet extraction) 24 hours, and with washing with acetone 24 hours, and dry and obtain the product of orange solids form under vacuum.GPC(CHCl
3)Mn(13,000g/mol)，Mw(24,700g/mol)。λ
Max482nm (solid film).
1H NMR is the same as expected.
Embodiment 4
Polymkeric substance 9 is by following described the preparation:
3,6-dioctyl thieno-[3,2-b] thiophene:
With 3, and 6-two bromos-thieno-[3,2-b] thiophene (referring to Fuller, L.S.; Iddon, B.; Smith, K.A.J.Perkin Trans.1,1997, the 3465 pages) (1.0g, 3.35mmol) and (1,1 '-two (diphenylphosphino) ferrocene) Palladous chloride (II) (10mg 0.014mmol) adds and is equipped with in the tubular vial of 20ml of stirring rod.This tubular vial of sealing is used purging with nitrogen gas then securely.Add THF (2ml) and octyl group zinc bromide (the 0.5M THF solution of 16.8mL), and 25 ℃ of following reaction stirred 3 minutes.Heated mixt is 7 minutes in the microwave reactor under 150 ℃ (EmrysCreator, Personal Chemistry Ltd).The cooling reactant, with MTBE (20ml) dilution and with 5% HCl (10ml), water (3 * 10ml), salt solution (10m) washing, dry (sodium sulfate) filters and under reduced pressure concentrated.By at silicon-dioxide (elutriant: gasoline) go up to filter and to be further purified this roughage, and from ethanol, make gained waxy solid recrystallization and obtain the product of pale yellow solid form.M/Z 364(M
+)。Find C, 72.3; H, 9.7, C
22H
36S
2Calculated value is C, 72.5; H, 9.9.
1H NMR (300MHz, CDCl
3) δ 8.95 (2H, s), 2.70 (4H, t), 1.74 (4H, quintets), 1.31 (20H, m), 0.88 (6H, t).
13C NMR(75MHz，CDCl
3)δ139.3，135.5，120.8，31.9，29.8，29.42，29.37，29.2，28.8，22.7，14.1。
2,5-two bromos-3,6-dioctyl thieno-[3,2-b] thiophene:
Added N-bromosuccinimide (1.95g, 11mmo l) portioning under 5 ℃ 3 in 1 hour, (2.0g is 5.5mmol) in the solution in Glacial acetic acid (50ml) and chloroform (50ml) for 6-dioctyl thieno-[3,2-b] thiophene.This solution of 20 ℃ of following restir 24 hours.Under reduced pressure remove and desolvate, and be suspended in resistates among the MTBE (100ml) and filter to remove the succinimide by product.Water (50ml), 5% Na
2CO
3(50ml), water (50ml) washs organic filtrate, dry (sodium sulfate) filters and under reduced pressure concentrates.(elutriant: gasoline) be further purified resistates and obtain yellow oil, it is crystallization when leaving standstill by filtering silicon-dioxide.HRMS 520.0472 (C
22H
34S
2Br
79 2Calculated value is 520.0469).
1H NMR (300MHz, CDCl
3) δ 2.66 (4H, t), 1.65 (4H, quintets), 1.29 (20H, m), 0.87 (6H, t).
13C NMR(75MHz，CDCl
3)δ136.1，134.4，109.4，31.9，29.32，29.27，29.19，28.1，22.7，14.1。
Poly-(3,6-dioctyl thieno-[3,2-b] thiophene-altogether-thieno-[3,2-b] thiophene) (9):
With 2,5-two bromos-3,6-dioctyl thieno-[3,2-b] thiophene (157mg, 0.3mmol), 2, two trimethylammonium stannyl thieno-[3, the 2-b] thiophene (140mg of 5-, 0.3mmol), tetrakis triphenylphosphine palladium (0) (5.0mg, 1.4mol%) and chlorobenzene (4.5ml) add and to be equipped with in the tubular vial of 10ml of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, PersonalChemistry Ltd) and heated 10 minutes to 200 ℃.In a single day only reach this temperature, just calculate elapsed time.After being cooled to RT, reaction mixture being precipitated in the mixture of methyl alcohol (50ml) and concentrated hydrochloric acid (2ml) and and stirring 16 hours down at 20 ℃.Filter out precipitation, and respectively extracted this precipitation 12 hours with methyl alcohol (soxhlet's extractor) and acetone (soxhlet's extractor).At last this polymkeric substance is dissolved in the warm chlorobenzene, filtration also precipitates in methyl alcohol.Collect this polymkeric substance and the dry 132mg product that obtains under vacuum by centrifugation.GPC(CHCl
3)Mn(3,200g/mol)，Mw(4,500g/mol)。λ
Max445nm (solid film).
1H NMR is the same as expected.
Embodiment 5
Polymkeric substance 10 is by following described the preparation:
Poly-(3,6-dioctyl thieno-[3,2-b] thiophene-altogether-thiophene) (9):
With 2,5-two bromos-3,6-dioctyl thieno-[3,2-b] thiophene (157mg, 0.3mmol), 2, two (trimethylammonium stannyl) thiophene of 5-(123mg, 0.3mmol), tetrakis triphenylphosphine palladium (0) (5.0mg, 1.4mol%) and chlorobenzene (4.5ml) adding be equipped with in the tubular vial of 10ml of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, PersonalChemistry Ltd) and heated 10 minutes to 200 ℃.In a single day only reach this temperature, just calculate elapsed time.After being cooled to RT, reaction mixture being precipitated in the mixture of methyl alcohol (50ml) and concentrated hydrochloric acid (2ml) and and stirring 16 hours down at 20 ℃.Filtering-depositing, and respectively extracted this precipitation 12 hours with methyl alcohol (soxhlet extraction) and acetone (soxhlet extraction), dry and obtain the 102mg product under vacuum then.GPC(CHCl
3)Mn(8,800g/mol)，Mw(20,800g/mol)。λ
Max528nm (solid film).
1H NMR(300MHz，CDCl
3，50℃)δ7.16(s，2H)，3.00(br t，4H)，1.80(m，4H)，1.40-1.20(m，20H)，0.90(t，6H)。
Embodiment 6
Polymkeric substance 11 is by following described the preparation:
Poly-(3,6-dioctyl thieno-[3,2-b] thiophene-altogether-bithiophene) (11):
With 2,5-two bromos-3,6-dioctyl thieno-[3,2-b] thiophene (157mg, 0.3mmol), 5,5 '-two (trimethylammonium stannyl)-[2,2 '] bithiophene (148mg, 0.3mmol), tetrakis triphenylphosphine palladium (0) (5.0mg, 1.4mol%) and chlorobenzene (4.5ml) add and to be equipped with in the tubular vial of 10ml of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, PersonalChemistry Ltd) and heated 10 minutes to 200 ℃.In a single day only reach this temperature, just calculate elapsed time.After being cooled to RT, reaction mixture being precipitated in the mixture of methyl alcohol (50ml) and concentrated hydrochloric acid (2ml) and and stirring 16 hours down at 20 ℃.Filter out precipitation, and respectively extracted this precipitation 12 hours with methyl alcohol (soxhlet's extractor) and acetone (soxhlet's extractor).At last this polymkeric substance is dissolved in the warm chlorobenzene, filtration also precipitates in methyl alcohol.Collect this polymkeric substance and the dry 144mg product that obtains under vacuum by centrifugation.GPC(CHCl
3)Mn(6,000g/mol)，Mw(10,000g/mol)。λ
Max511nm (solid film).
1H NMR is the same as expected.
Embodiment 7
Polymkeric substance 12 is by following described the preparation:
3,6-two (dodecyl) thieno-[3,2-b] thiophene:
With 3, and 6-two bromo thieno-s [3,2-b] thiophene (1.00g, 3.36mmol) and Pd (dppf) Cl
2(0.14g, 0.17mmol 5mol%) add in the tubular vial of 20mL, and with purging with nitrogen gas 10 minutes.The dodecyl bromination zinc that adds 0.5M is at anhydrous THF (15mL, 7.5mmol) solution in.Should tubular vial put in the microwave reactor (Emrys Creator, PersonalChemistry Ltd) and 150 ℃ and stir under heating 10 minutes.After being cooled to RT, with ether (100mL) reaction mixture being diluted, and stop with 5% hydrochloric acid (50mL).Separate organic layer and come aqueous layer extracted again with ether (100mL).The extract that water (2 * 50 milliliters) washing merges, dry and concentrated in a vacuum on sodium sulfate.With the short packing of this crude product filtration silicon-dioxide, with sherwood oil 40-60 wash-out.Recrystallization obtains the product of pale yellow solid form from 2-butanone.
1H NMR(300MHz，CDCl
3)δ6.95(s，2H)，2.70(t，4H)，1.74(m，4H)，1.22-1.42(br，36H)，0.88(t，6H)。
13C NMR(75MHz，CDCl
3)δ139.3，135.5，120.8，31.9，29.8，29.69，29.67，29.6，29.42，29.37，28.7，22.7，14.2。
2,5-two bromos-3,6-two (dodecyl) thieno-[3,2-b] thiophene:
With 3, (2.00g 4.19mmol) adds in the three-necked flask and uses purging with nitrogen gas 6-two (dodecyl) thieno-[3,2-b] thiophene.Add anhydrous THF (20mL) and this solution is cooled to 0 ℃.(1.57g, 8.81mmol) portioning adds with NBS in during 20 minutes.0 ℃ of following stirred reaction mixture 1 hour, under RT, stirred 16 hours then.Pour into reaction mixture among the sherwood oil 40-60 (200mL) and leach precipitation.In a vacuum filtrate is concentrated and obtained crude product.By column chromatography (elutriant: purifying sherwood oil 40-60), then recrystallization and obtain the product of white solid form from 2-butanone.
1H NMR(300MHz，CDCl
3)δ2.67(t，4H)，1.66(m，4H)，1.22-1.42(br，36H)，0.88(t，6H)。
13C NMR(75MHz，CDCl
3)δ136.1，134.4，109.4，31.9，29.67，29.65，29.5，29.37，29.34，29.26，28.9，28.1，22.7，14.2。
Poly-(3,6-two (dodecyl) thieno-[3,2-b] thiophene-altogether-thiophene) (12):
With 2,5-two bromos-3,6-two (dodecyl) thieno-[3,2-b] thiophene (127mg, 0.2mmol), 2, two (trimethylammonium stannyl) thiophene of 5-(82mg, 0.2mmol), Pd
2(dba)
3(4mg, 0.004mmol, 4mol%Pd), P (o-tol)
3(3mg, 0.010mmol, 5mol%), LiCl (9mg, 0.2mmol) and chlorobenzene (5mL) add and to be equipped with in the tubular vial of 10ml of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, Personal Chemistry Ltd) and 200 ℃ and stir under heating 10 minutes.After being cooled to RT, reaction mixture being precipitated in the mixture of hydrochloric acid (5mL) of acetone (50mL) and 37%, and stirring 1 hour.Leach polymkeric substance, use washing with acetone, and dry under vacuum.With washing with acetone (passing through soxhlet extraction) polymkeric substance 18 hours with sherwood oil 40-60 washing 6 hours, and dry and obtain the product (100mg, 89%) of dark red solid form under vacuum.GPC(CHCl
3)Mn(8,100g/mol)，Mw(16,500g/mol)。λ
Max550nm (solid film).
1H NMR is the same as expected.
Embodiment 8
Polymkeric substance 13 is by following described the preparation:
Poly-(3,6-two (dodecyl) thieno-[3,2-b] thiophene-altogether-bithiophene) (13):
With 2,2 '-two bromos-3,3-two (dodecyl) thieno-[3,2-b] thiophene (127mg, 0.2mmol), 5,5 '-two (trimethylammonium stannyls)-2,2 '-bithiophene (98mg, 0.2mmol), Pd
2(dba)
3(4mg, 0.004mmol, 4mol%Pd), P (o-tol)
3(3mg, 0.010mmol, 5mol%), LiCl (9mg, 0.2mmol) and chlorobenzene (5mL) add and to be equipped with in the tubular vial of 10mL of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, Personal Chemistry Ltd) and 200 ℃ and stir under heating 10 minutes.After being cooled to RT, reaction mixture being precipitated in the mixture of hydrochloric acid (5mL) of acetone (50mL) and 37%, and stirring 1 hour.Leach polymkeric substance, use washing with acetone, and dry under vacuum.Washed (passing through soxhlet extraction) polymkeric substance respectively 18 hours and 6 hours with acetone and sherwood oil 40-60, and dry and obtain the product (96mg, 75%) of dark red solid form under vacuum.GPC(CHCl
3)Mn(9,300g/mol)，Mw(16,000g/mol)。λ
Max530nm (solid film).
1H NMR is the same as expected.
Embodiment 9
Polymkeric substance 14 is by following described the preparation:
Poly-(3,6-two (dodecyl) thieno-[3,2-b] thiophene-altogether-thieno-[3,2-b] thiophene) (14):
With 2,5-two bromos-3,6-two (dodecyl) thieno-[3,2-b] thiophene (127mg, 0.2mmol), 2, two (trimethylammonium stannyl) thieno-[3, the 2-b] thiophene of 5-(93mg, 0.2mmol), Pd
2(dba)
3(4mg, 0.004mmol, 4mol%Pd), P (o-tol)
3(3mg, 0.010mmol, 5mol%), LiCl (9mg, 0.2mmol) and chlorobenzene (5ml) add and to be equipped with in the tubular vial of 10ml of stirring rod.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, PersonalChemistry Ltd) and heated 10 minutes to 200 ℃.After being cooled to RT, reaction mixture being precipitated in the mixture of hydrochloric acid (5mL) of acetone (50mL) and 37%, and stirring 1 hour.Leach polymkeric substance, use washing with acetone, and dry under vacuum.Washed (passing through soxhlet extraction) polymkeric substance respectively 18 hours and 6 hours with acetone and sherwood oil 40-60, and dry and obtain the product (98mg, 80%) of red solid form under vacuum.GPC(CHCl
3)Mn(5,400g/mol)，Mw(6,800g/mol)。λ
Max463nm (solid film).
1H NMR is the same as expected.
Embodiment 10
Polymkeric substance 15 is by following described the preparation:
Poly-(3,6-two (dodecyl) thieno-[3,2-b] thiophene-altogether-selenophen) (15):
With 2,5-two bromos-3,6-two (dodecyl) thieno-[3,2-b] thiophene (127mg, 0.2mmol), 2, the two trimethylammonium stannyl selenophens of 5-(91mg, 0.2mmol), Pd
2(dba)
3(4mg, 0.004mmol, 4mol%Pd), P (o-tol)
3(8mol%) adding is equipped with in the tubular vial of 10ml of stirring rod with anhydrous THF (4ml) for 5mg, 0.016mmol.With this tubular vial of purging with nitrogen gas and sealing securely.Should tubular vial put in the microwave reactor (Emrys Creator, Personal Chemistry Ltd) and heated 10 minutes to 150 ℃.After being cooled to RT, reaction mixture being precipitated in the mixture of hydrochloric acid (5mL) of methyl alcohol (50mL) and 37%, and stirring 1 hour.Leach polymkeric substance, use methanol wash, and dry under vacuum.Washed (passing through soxhlet extraction) polymkeric substance respectively 8 hours and 8 hours with acetone and sherwood oil 40-60, and dry and obtain the product of dark red solid form under vacuum.GPC(CHCl
3)Mn(6,300g/mol)，Mw(9,300g/mol)。λ
Max572nm (solid film).
1H NMR is the same as expected.
Embodiment 11-transistor is made and is measured
At the hot growing silicon oxide (SiO of having of high doped
2) make film organic field effect tube (OFET) on the silicon substrate of insulation layer, wherein this substrate plays common gate electrode.At this SiO
2Limit source transistor-leakage gold electrode with photolithographicallpatterned on the layer.Before the organic semiconductor deposition, handle the FET substrate with silane-based agent hexamethyldisilazane (HMDS).Then by coming the deposited semiconductor film at the solution (0.4-1.0wt%) of spin on polymers on the FET substrate in chloroform, dimethylbenzene, chlorobenzene or dichlorobenzene.The Agilent 4155C analyzing parameters of semiconductor instrument of control of using a computer carries out the electrical characterization of transistor device under ambiance.
On the film for preparing by spin coating, measure the transistor characteristic (table 1) of embodiment 1-3 (compound 3,7 and 8) and embodiment 5-10 (compound 10-15).Under nitrogen, film is heated 10 minutes to 100 ℃ to remove residual solvent, be cooled to room temperature then to measure transistor characteristic.Transmission and the output characteristic of embodiment 2 (compound 7) are shown in Figure 1.Device shows linearity and the saturated mode that typically has synthetic p-type behavior of good electric current and perfect definition.Use formula (1) to calculate at saturated mode (V
d＞(V
g-V
0)) under field-effect mobility:
Wherein, W is a passage width, and L is a passage length, C
iBe the electric capacity of insulation layer, V
gBe grid voltage, V
dBe drain voltage, I
dBe drain current, V
0Be to connect voltage, μ
SatIt is saturated carrier mobility.Connect voltage (V
0) be determined as the initial value (Fig. 1) of source-drain electrodes electric current.
Table 1-transistor characteristic
| Material | Saturated mobility (μ sat) | The on/off ratio |
| 3 7 8 10 11 12 13 14 15 | 1.0×10 -6cm 2/Vs 8.8×10 -2cm/Vs 1.7×10 -5cm 2/Vs 4.3×10 -3cm 2/Vs 2.0×10 -3cm 2/Vs 5.2×10 -2cm 2/Vs 4.2×10 -2cm 2/Vs 1.0×10 -3cm 2/Vs 6.5×10 -2cm 2/Vs | 1×10 4 1×10 6 1×10 4 1×10 4 1×10 4 3×10 5 1×10 7 1×10 4 1×10 6 |
Claims (13)
1. comprise at least one thieno-[3,2-b] thiophene-2, monomer, oligopolymer and the polymkeric substance of 5-two bases (TT) group, it is characterized in that they comprise at least one at the substituted TT group of 3-and 6-position and/or at least one is at 3-and/or 4-position substituted thiophene-2,5-two bases or selenophen-2,5-two bases.
2. according to monomer, oligopolymer and the polymkeric substance of claim 1, it is characterized in that they are compounds of general formula I
-([A]
a-[B]
b-[C]
c-[D]
d)
n- I
Wherein A and C are independently of one another:
B and D are-CX independently of one another
1=CX
2,-C ≡ C-or optional by one or more radicals R
1The arylidene or the heteroarylidene that replace,
R
1And R
2Represent H independently of one another; Halogen; Optional substituted aryl or heteroaryl; Or containing straight chain, branching or the cyclic alkyl of 1 to 20 C atom, they can be unsubstituted, are replaced or polysubstituted by F, Cl, Br, I or CN are single, also may wherein one or more non-conterminous CH
2Group in each case independently of one another by-O-,-S-,-NH-,-NR
0-,-SiR
0R
00-,-CO-,-COO-,-OCO-,-O-CO-O-,-S-CO-,-CO-S-,-CX
1=CX
2-or-C ≡ C-substitutes and satisfies O and/or the S atom is not directly to connect each other,
X
1And X
2Be H, F, Cl or CN independently of one another,
R
0And R
00Be H independently of one another, contain the alkyl of 1 to 12 C atom, or aryl,
A and c are 0 or 1 independently of one another, wherein at least one group [(A)
a-(B)
b-(C)
c-(D)
d] in, a and/or c are 1,
B and d are 0,1 or 2 independently of one another,
N is 1 to 10,000 integer,
Wherein under the situation of n＞1, group [(A)
a-(B)
b-(C)
c-(D)
d] can be identical or different, and precondition is
A) this compound comprises at least one by radicals R
1And R
2The group A or the C that replace, radicals R
1And R
2Have at least 3 C atoms separately, and/or
B) this compound comprises at least one group B or D, and this B or D are the radicals R that is different from H in 3-and/or 4-position
1The thiophene-2 that replaces, 5-two bases or selenophen-2,5-two bases.
3. according to monomer, oligopolymer and the polymkeric substance of claim 2, it is characterized in that they are compounds of general formula I 1
R
3-[(A)
a-(B)
b-(C)
c-(D)
d]
n-R
4 I1
R wherein
1, R
2, a, b, c, d and n have independently of one another one of implication in the claim 2 and
R
3And R
5Be H, C independently of one another
1-C
12Alkyl, halogen, Sn (R
0)
3, B (OR
0)
2, CH
2Cl, COH, CH=CH
2, SiR
0R
00R
000Or optional aryl or the heteroaryl that replaces, wherein R
0And R
00Have implication and R in the claim 2
000Has R
00One of implication.
4. according at least one monomer, oligopolymer and polymkeric substance in the claim 1 to 3, it is characterized in that they have 10 to 5000 the polymerization degree (n).
5. according at least one monomer, oligopolymer and polymkeric substance in the claim 2 to 4, wherein R
1And R
2Be selected from: the optional C that is replaced by one or more fluorine atoms
3-C
20Alkyl, C
3-C
20Alkenyl, C
3-C
20Alkynyl, C
3-C
20Ester, C
3-C
20Amino, C
3-C
20Fluoro-alkyl and optional aryl or the heteroaryl that replaces.
6. according at least one monomer in the claim 2 to 5, oligopolymer and polymkeric substance, wherein B and C are selected from 1, the 4-phenylene, fluorizated 1, the 4-phenylene, 2, the 5-pyridine, 2, the 5-pyrimidine, p, p '-xenyl, naphthalene-2,6-two bases, thiophene-2,5-two bases, selenophen-2,5-two bases, fluoridize or alkylating thiophene-2 5-two bases or selenophen-2,5-two bases, 2,2 '-two thiophene, fluoridize or alkylating 2,2 '-two thiophene, fluorizated benzo [1,2-b:4,5-b '] two thiophene, 2, the 5-thiazole, 2, the 5-thiadiazoles, 2,5- azoles and 2,5- diazole, all these groups are unsubstituted, single or polysubstituted by L, wherein L is F, Cl, Br or have the alkyl of 1 to 12 C atom, alkoxyl group, alkyl-carbonyl or alkoxy carbonyl, wherein one or more H atoms are randomly substituted by F or Cl.
7. according at least one monomer, oligopolymer and polymkeric substance in the claim 2 to 6, wherein [(A)
a-(B)
b-(C)
c-(D)
d]
n-be selected from following general formula:
Wherein n has one of implication in the general formula I and R has in the general formula I R
1One of implication that provides.
8. according at least one monomer in the claim 1 to 7, oligopolymer and polymkeric substance are as charge transfer, characteristic of semiconductor, conduction, photoconductivity or luminescent material, at optics, electrooptics or electronic component or device, organic field effect tube (OFET), unicircuit (IC), thin film transistor (TFT), flat-panel monitor, RF identification (RFID) label, electroluminescent or photo luminescent devices or element, Organic Light Emitting Diode (OLED), the backlight of indicating meter, photovoltaic or sensor component, electric charge injection layer, schottky diode, complanation layer, antistatic film, conductive substrate or pattern, electrode materials in the battery, optical conductor, electrofax is used, electrophotographic recording, organic memory device, both alignment layers, the purposes in makeup or the pharmaceutical composition, or be used to detect and differentiate the purposes of dna sequence dna.
9. comprise according at least one optics, electrooptics or electron device, FET, unicircuit (IC), TFT, OLED or the both alignment layers of material in the claim 1 to 7.
10. comprise according in the claim 1 to 7 at least one material or according to the TFT that is used for flat-panel monitor or tft array, RF identification (RFID) label, electroluminescent display or the backlight of FET, IC, TFT or the OLED of claim 9.
11. comprise according to the FET of claim 9 or 10 or the safety label or the device of RFID label.
12. the monomer, oligopolymer and the polymkeric substance that limit at least one in the claim 1 to 7, it mixes and forms conductive ion type material through oxidation or reduction mode.
13. be used for electric charge injection layer, complanation layer, antistatic film or conductive substrate or the pattern of electronic application or flat-panel monitor, it comprises monomer, oligopolymer or polymkeric substance according to claim 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04011713 | 2004-05-18 | ||
| EP04011713.7 | 2004-05-18 | ||
| PCT/EP2005/004271 WO2005111045A1 (en) | 2004-05-18 | 2005-04-21 | MONO-, OLIGO- AND POLYTHIENO[3,2-b]THIOPHENES |
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| CN1956988B CN1956988B (en) | 2014-03-26 |
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| CN200580015968.0A Active CN1956988B (en) | 2004-05-18 | 2005-04-21 | Mono-, oligo- and polythieno[3,2-b]thiophenes |
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| CN201210057765XA Pending CN102702486A (en) | 2004-05-18 | 2005-04-21 | Mono-, oligo- and polythieno [3,2-b] thiophenes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102227483A (en) * | 2008-11-28 | 2011-10-26 | 剑桥显示技术有限公司 | Organic semiconductors |
| CN102448950A (en) * | 2009-05-28 | 2012-05-09 | 康宁股份有限公司 | Fused thiophenes, articles, and methods thereof |
| CN102448950B (en) * | 2009-05-28 | 2014-08-06 | 康宁股份有限公司 | Fused thiophenes, articles, and methods thereof |
| CN109307964A (en) * | 2017-07-28 | 2019-02-05 | 京东方科技集团股份有限公司 | Broken wire repair method, substrate and display device |
| US11302723B2 (en) | 2017-07-28 | 2022-04-12 | Boe Technology Group Co., Ltd. | Electrical connection method, substrate and display device |
| US11404648B2 (en) | 2018-07-27 | 2022-08-02 | Wuhan Tianma Microelectronics Co., Ltd | Aromatic heterocyclic compound and organic light-emitting display device |
| CN110922983A (en) * | 2018-09-20 | 2020-03-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing dibenzothiophene polymerizable monomer and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1751166A1 (en) | 2007-02-14 |
| JP2008504379A (en) | 2008-02-14 |
| WO2005111045A1 (en) | 2005-11-24 |
| TW200611918A (en) | 2006-04-16 |
| ATE446961T1 (en) | 2009-11-15 |
| JP5546727B2 (en) | 2014-07-09 |
| CN102702486A (en) | 2012-10-03 |
| TWI371457B (en) | 2012-09-01 |
| US7714098B2 (en) | 2010-05-11 |
| KR20070018072A (en) | 2007-02-13 |
| CN1956988B (en) | 2014-03-26 |
| KR101209378B1 (en) | 2012-12-06 |
| DE602005017384D1 (en) | 2009-12-10 |
| EP1751166B1 (en) | 2009-10-28 |
| US20070232812A1 (en) | 2007-10-04 |
| JP2014062254A (en) | 2014-04-10 |
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